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Although selected configuration interaction (SCI) algorithms can tackle much larger Hilbert spaces than the conventional full CI method, the scaling of their computational cost with respect to the system size remains inherently exponential. In addition, inaccuracies in describing the correlation hole at small interelectronic distances lead to the slow convergence of the electronic energy relative to the size of the one-electron basis set. To alleviate these effects, we show that the non-Hermitian, transcorrelated (TC) version of SCI significantly compactifies the determinant space, allowing us to reach a given accuracy with a much smaller number of determinants. Furthermore, we note a significant acceleration in the convergence of the TC-SCI energy as the basis set size increases. The extent of this compression and the energy convergence rate are closely linked to the accuracy of the correlation factor used for the similarity transformation of the Coulombic Hamiltonian. Our systematic investigation of small molecular systems in increasingly large basis sets illustrates the magnitude of these effects., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Electronic resonances are metastable states that can decay by electron loss. They are ubiquitous across various fields of science, such as chemistry, physics, and biology. However, current theoretical and computational models for resonances cannot yet rival the level of accuracy achieved by bound-state methodologies. Here, we generalize selected configuration interaction (SCI) to treat resonances by using the complex absorbing potential (CAP) technique. By modifying the selection procedure and the extrapolation protocol of standard SCI, the resulting CAP-SCI method yields resonance positions and widths of full configuration interaction quality. Initial results for the shape resonances of N 2 - and CO - reveal the important effect of high-order correlation, which shifts the values obtained with CAP-augmented equation-of-motion coupled-cluster with singles and doubles by more than 0.1 eV. The present CAP-SCI approach represents a cornerstone in the development of highly accurate methodologies for resonances.

In an effort to expand the existing QUEST database of accurate vertical transition energies [Véril et al. WIREs Comput. Mol. Sci. 2021, 11, e1517], we have modeled more than 100 electronic excited states of different natures (local, charge-transfer, Rydberg, singlet, and triplet) in a dozen of mono- and di-substituted benzenes, including aniline, benzonitrile, chlorobenzene, fluorobenzene, nitrobenzene, among others. To establish theoretical best estimates for these vertical excitation energies, we have employed advanced coupled-cluster methods including iterative triples (CC3 and CCSDT) and, when technically possible, iterative quadruples (CC4). These high-level computational approaches provide a robust foundation for benchmarking a series of popular wave function methods. The evaluated methods all include contributions from double excitations (ADC(2), CC2, CCSD, CIS(D), EOM-MP2, STEOM-CCSD), along with schemes that also incorporate perturbative or iterative triples (ADC(3), CCSDR(3), CCSD(T)(a)   ⋆ , and CCSDT-3). This systematic exploration not only broadens the scope of the QUEST database but also facilitates a rigorous assessment of different theoretical approaches in the framework of a homologous chemical series, offering valuable insights into the accuracy and reliability of these methods in such cases. We found that both ADC(2.5) and CCSDT-3 can provide very consistent estimates, whereas among less expensive methods SCS-CC2 is likely the most effective approach. Importantly, we show that some lower order methods may offer reasonable trends in the homologous series while providing quite large average errors, and vice versa. Consequently, benchmarking the accuracy of a model based solely on absolute transition energies may not be meaningful for applications involving a series of similar compounds., (© 2024 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.)

Upon ionization of an atom or a molecule, another electron (or more) can be simultaneously excited. These concurrently generated states are called "satellites" (or shakeup transitions) as they appear in ionization spectra as higher-energy peaks with weaker intensity and larger width than the main peaks associated with single-particle ionizations. Satellites, which correspond to electronically excited states of the cationic species, are notoriously challenging to model using conventional single-reference methods due to their high excitation degree compared to the neutral reference state. This work reports 42 satellite transition energies and 58 valence ionization potentials (IPs) of full configuration interaction quality computed in small molecular systems. Following the protocol developed for the quest database [Véril, M.; Scemama, A.; Caffarel, M.; Lipparini, F.; Boggio-Pasqua, M.; Jacquemin, D.; and Loos, P.-F. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2021, 11, e1517], these reference energies are computed using the configuration interaction using a perturbative selection made iteratively (CIPSI) method. In addition, the accuracy of the well-known coupled-cluster (CC) hierarchy (CC2, CCSD, CC3, CCSDT, CC4, and CCSDTQ) is gauged against these new accurate references. The performances of various approximations based on many-body Green's functions ( GW , GF2, and T -matrix) for IPs are also analyzed. Their limitations in correctly modeling satellite transitions are discussed.

Selected configuration interaction (SCI) methods have emerged as state-of-the-art methodologies for achieving high accuracy and generating benchmark reference data for ground and excited states in small molecular systems. However, their precision relies heavily on extrapolation procedures to produce a final estimate of the exact result. Using the structure of the exact electronic energy landscape, we provide a rationale for the common linear extrapolation of the variational energy as a function of the second-order perturbative correction. In particular, we demonstrate that the energy gap and the coupling between the so-called internal and external spaces are the key factors determining the rate at which the linear regime is reached. Starting from the first principles, we also derive a new non-linear extrapolation formula that improves the post-processing of data generated from SCI methods and can be applied to both ground- and excited-state energies., (© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)

Molecules that violate Hund's rule and exhibit an inverted gap between the lowest singlet S 1 and triplet T 1 excited states have attracted considerable attention due to their potential applications in optoelectronics. Among these molecules, the triangular-shaped heptazine, and its derivatives, have been in the limelight. However, conflicting reports have arisen regarding the relative energies of S 1 and T 1 . Here, we employ highly accurate levels of theory, such as CC3, to not only resolve the debate concerning the sign but also quantify the magnitude of the S 1 -T 1 gap. We also determined the 0-0 energies to evaluate the significance of the vertical approximation. In addition, we compute reference S 1 -T 1 gaps for a series of 10 related molecules. This enables us to benchmark lower-order methods for future applications in larger systems within the same family of compounds. This contribution can serve as a foundation for the design of triangular-shaped molecules with enhanced photophysical properties.

We derive the explicit expression of the three self-energies that one encounters in many-body perturbation theory: the well-known GW self-energy, as well as the particle-particle and electron-hole T-matrix self-energies. Each of these can be easily computed via the eigenvalues and eigenvectors of a different random-phase approximation linear eigenvalue problem that completely defines their corresponding response function. For illustrative and comparative purposes, we report the principal ionization potentials of a set of small molecules computed at each level of theory. The performance of these schemes on strongly correlated systems (B2 and C2) is also discussed., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

The geometries and UV-vis spectra of azobenzene dyes grafted as a side chain on poly(l-glutamic acid) have been investigated using a combination of quantum mechanics/molecular mechanics (QM/MM) and time-dependent density functional theory (TD-DFT) methods at the TD-PBE0/6-311+G(d,p)//B3LYP/6-311G(d,p):Amber ff99 level of theory. The influence of the secondary structure of the polypeptide on the electronic properties of both the trans and cis conformations of azobenzene dyes has been studied. It turns out that the grafted dyes exhibit a red-shift of the π → π* absorption energies mainly due to the auxochromic shift induced by the peptidic group used to link the chromophoric unit to the polypeptide and that specific interactions between the glutamic side chain and the azobenzene moiety lead to a large blue-shift of the n → π* transition.